WO2016152099A1 - 製鋼スラグからカルシウムを含有する固体成分を回収する方法、および回収された固体成分 - Google Patents

製鋼スラグからカルシウムを含有する固体成分を回収する方法、および回収された固体成分 Download PDF

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WO2016152099A1
WO2016152099A1 PCT/JP2016/001492 JP2016001492W WO2016152099A1 WO 2016152099 A1 WO2016152099 A1 WO 2016152099A1 JP 2016001492 W JP2016001492 W JP 2016001492W WO 2016152099 A1 WO2016152099 A1 WO 2016152099A1
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Prior art keywords
aqueous solution
calcium
slag
solid component
steelmaking slag
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PCT/JP2016/001492
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English (en)
French (fr)
Japanese (ja)
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康 福居
昭広 浅場
正一 松尾
山本　雅也
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日新製鋼株式会社
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Priority to CA2980419A priority Critical patent/CA2980419A1/en
Priority to US15/560,711 priority patent/US10287652B2/en
Priority to MYPI2017703536A priority patent/MY182970A/en
Priority to KR1020177024574A priority patent/KR20170130394A/ko
Priority to MX2017012201A priority patent/MX2017012201A/es
Priority to BR112017020090-2A priority patent/BR112017020090A2/pt
Priority to CN201680016728.0A priority patent/CN107406318A/zh
Priority to EP16768006.5A priority patent/EP3275848A4/en
Priority to RU2017133114A priority patent/RU2695173C2/ru
Publication of WO2016152099A1 publication Critical patent/WO2016152099A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F5/00—Compounds of magnesium
    • C01F5/24—Magnesium carbonates
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/04—Working-up slag
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/18—Carbonates
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B5/00—Treatment of  metallurgical  slag ; Artificial stone from molten  metallurgical  slag 
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B5/00—Treatment of  metallurgical  slag ; Artificial stone from molten  metallurgical  slag 
    • C04B5/06—Ingredients, other than water, added to the molten slag or to the granulating medium or before remelting; Treatment with gases or gas generating compounds, e.g. to obtain porous slag
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B3/00—General features in the manufacture of pig-iron
    • C21B3/04—Recovery of by-products, e.g. slag
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C5/00—Manufacture of carbon-steel, e.g. plain mild steel, medium carbon steel or cast steel or stainless steel
    • C21C5/28—Manufacture of steel in the converter
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • C22B7/008—Wet processes by an alkaline or ammoniacal leaching
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B2400/00—Treatment of slags originating from iron or steel processes
    • C21B2400/02—Physical or chemical treatment of slags
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies

Definitions

  • the present invention relates to a method for recovering a solid component containing calcium from steelmaking slag, and a solid component recovered by the recovery method.
  • Steelmaking slag (converter slag, pretreatment slag, secondary refining slag, electric furnace slag, etc.) generated in the steelmaking process includes phosphorus (P), calcium (Ca), iron (Fe), silicon (Si), manganese ( It is known that oxides such as Mn), magnesium (Mg), and aluminum (Al) are contained.
  • calcium is the free lime (CaO) introduced in the steelmaking process as it is or remains as free lime deposited in the solidification process, or the free lime reacts with water vapor or carbon dioxide in the air. And formed as calcium hydroxide (Ca (OH) 2 ) or calcium carbonate (CaCO 3 ).
  • Steelmaking slag is used in a wide range of applications including cement materials, roadbed materials, civil engineering materials, and fertilizers (see Non-Patent Documents 1 to 3).
  • the free lime contained in the steelmaking slag needs to be handled with care because it causes the product to expand or elute as highly alkaline water when it comes into contact with water (see Non-Patent Document 1).
  • calcium is used as a calcium carbonate in the iron making sintering process. Moreover, it is used at a steelmaking process as calcium oxide obtained by baking calcium. In addition, calcium hydroxide obtained by adding water to calcium oxide is used as a neutralizing agent such as an acid in the drainage process. Therefore, if calcium can be recovered from the steelmaking slag generated in the ironmaking process, the calcium can be reused and the cost of ironmaking can be reduced.
  • Patent Document 1 describes a method of recovering precipitated calcium carbonate by blowing carbon dioxide into an aqueous solution from which calcium in converter slag has been eluted. At this time, in order to suppress the production of calcium bicarbonate having high solubility in water, the lower limit of pH is maintained at about 10. Patent Document 1 does not describe a specific method for maintaining the pH at 10 or more. However, when this method is performed, the pH is maintained at 10 or more by adjusting the amount of carbon dioxide blown. It seems to do.
  • Patent Document 2 the crushed steelmaking slag is separated into an iron-concentrated phase and a phosphorus-concentrated phase, and the calcium component in the phosphorus-concentrated phase is dissolved in washing water in which carbon dioxide is dissolved as calcium hydrogen carbonate. Is described in which calcium bicarbonate in washing water is precipitated as calcium carbonate by heating to about 50 to 60 ° C.
  • Patent Document 3 describes a method in which a calcium compound is eluted from steelmaking slag in a plurality of times.
  • this recovery method when the steelmaking slag (pretreatment slag) is immersed in water into which carbon dioxide has been blown, the 2CaO ⁇ SiO 2 phase and phosphorus dissolved in this phase are preferentially eluted. Is described.
  • the present invention provides a method for recovering a solid component containing calcium from steelmaking slag, which can easily increase the recovery rate of calcium, and a solid component containing calcium obtained by this recovery method
  • the purpose is to do.
  • a method for recovering a solid component containing calcium from steelmaking slag the first step of immersing the steelmaking slag in an aqueous solution containing carbon dioxide; A second step of separating the immersed steelmaking slag and the aqueous solution; A third step of increasing the pH of the aqueous solution separated from the steelmaking slag; And a fourth step of recovering the solid component precipitated in the aqueous solution having an increased pH.
  • the second of the present invention relates to the following solid components.
  • a method for recovering a solid component containing calcium from steelmaking slag which has a high calcium recovery rate and can be easily performed, so that the recovery cost is low.
  • recovery method is provided.
  • FIG. 1 is a flowchart of the first recovery method in the present invention.
  • FIG. 2 is a flowchart of the second recovery method in the present invention.
  • FIG. 3 is a flowchart of the third recovery method in the present invention.
  • FIG. 4 is a flowchart of the fourth recovery method in the present invention.
  • FIG. 1 is a flowchart of a method for recovering a solid component containing calcium according to an embodiment of the present invention (hereinafter also referred to as “first recovery method”).
  • the method for recovering a solid component containing calcium according to the present embodiment includes a step of immersing steelmaking slag in an aqueous solution containing carbon dioxide (step S110), the immersed steelmaking slag, and the A step of separating the aqueous solution (step S120), a step of raising the pH of the aqueous solution separated from the steelmaking slag (step S150), and a step of recovering the solid components precipitated in the aqueous solution (step S160).
  • a solid component containing a large amount of calcium derived from steelmaking slag can be recovered by a simpler method than before. Moreover, since the aqueous solution after being used for the first recovery method has a small content of calcium, manganese, phosphorus, etc., the wastewater treatment can be simplified or made unnecessary and the cost of the wastewater treatment can be suppressed. .
  • steelmaking slag may be immersed in water in which carbon dioxide has been dissolved in advance, or carbon dioxide may be dissolved in water after the steelmaking slag is immersed in water.
  • carbon dioxide may be dissolved in water after the steelmaking slag is immersed in water.
  • Carbon dioxide can be dissolved in water by, for example, bubbling (blowing) a gas containing carbon dioxide. From the viewpoint of enhancing calcium elution from steelmaking slag, it is preferable that 30 ppm or more of carbon dioxide is dissolved in the aqueous solution.
  • the gas containing carbon dioxide may be pure carbon dioxide gas or a gas containing components other than carbon dioxide (for example, oxygen or nitrogen).
  • the gas containing carbon dioxide include exhaust gas after combustion, and a mixed gas of carbon dioxide, air and water vapor. From the viewpoint of increasing the concentration of carbon dioxide in the aqueous solution and increasing the elution of calcium compounds (such as calcium silicate) from the steelmaking slag into the aqueous solution, the gas containing carbon dioxide has a high concentration of carbon dioxide (for example, 90%).
  • Steelmaking slag may be any slag discharged in the steelmaking process.
  • steelmaking slag include converter slag, pretreatment slag, secondary refining slag and electric furnace slag.
  • Steelmaking slag may be used as it is discharged in the steelmaking process, but may be used after being discharged and crushed.
  • the maximum particle size of the crushed steelmaking slag is preferably 1000 ⁇ m or less.
  • Steelmaking slag can be crushed to the said range with a well-known crusher.
  • the steelmaking slag may be further pulverized until the maximum particle size becomes 100 ⁇ m or less.
  • the steelmaking slag can be pulverized to the above range by, for example, a roller mill or a ball mill.
  • metallic iron may be removed from the steelmaking slag before immersion.
  • Metallic iron can be removed from the steelmaking slag by a known magnetic separator. From the viewpoint of increasing the removal efficiency of metallic iron, it is preferable to remove metallic iron after crushing steelmaking slag, and it is more preferable to remove metallic iron after crushing steelmaking slag.
  • the amount of slag in the aqueous solution is preferably 1 g / L or more and 100 g / L or less, and more preferably 2 g / L or more and 40 g / L or less.
  • the immersion is preferably performed for 3 minutes or more, and more preferably for 5 minutes or more.
  • Step S120 Separation of steelmaking slag and aqueous solution
  • the aqueous solution (supernatant solution) in which phosphorus and calcium are dissolved is separated from the steelmaking slag (step S120). Separation can be performed by a known method. Examples of the separation method include filtration and a method in which an aqueous solution is allowed to stand to precipitate steelmaking slag.
  • step S120 When calcium begins to precipitate, white turbidity due to calcium carbonate occurs in the aqueous solution. It is sufficient to raise the pH of the aqueous solution to such an extent that the white turbidity can be visually confirmed. From the viewpoint of more sufficiently precipitating calcium and increasing the recovery rate of calcium, it is preferable to raise the pH by 0.2 or more with respect to the pH of the aqueous solution separated from the steelmaking slag in the second step (step S120). , More preferably 0.3 or more, further preferably 1.0 or more, further preferably 1.5 or more, and further preferably 2.0 or more.
  • the pH of the aqueous solution can be measured by a known glass electrode method.
  • the pH of the aqueous solution can be raised, for example, by introducing an alkaline substance into the aqueous solution.
  • alkaline substances that can be introduced into the aqueous solution include calcium hydroxide, ammonia and sodium hydroxide.
  • calcium hydroxide, ammonia or sodium hydroxide When calcium hydroxide, ammonia or sodium hydroxide is added, a solution in which these substances are dissolved in water may be added to the aqueous solution.
  • Calcium hydroxide, ammonia and sodium hydroxide may be commercially available, or may be contained in waste liquid or other liquids.
  • a waste liquid produced when calcium carbide (calcium carbide) and water are reacted to produce acetylene can be added to the aqueous solution.
  • slag leaching water generated by immersing steelmaking slag in water may be added to the aqueous solution.
  • Slag leaching water may be obtained by immersing steelmaking slag from which calcium is to be recovered in water before the first step (step S110) (see the second recovery method described later).
  • Steelmaking slag may be obtained by immersing it in water.
  • the pH of the aqueous solution is increased by removing carbon dioxide as in the sixth step (step S130) described later, the removal of carbon dioxide is not included in the third step in the present invention.
  • the calcium recovery rate can be increased more than the removal of carbon dioxide by increasing the pH in the aqueous solution by introducing an alkaline substance or the like.
  • the aqueous solution after recovering calcium by the method of the present invention can simplify or eliminate the wastewater treatment, and suppress the cost of the wastewater treatment.
  • step S160 the solid component precipitated in the third step is collected (step S160).
  • the precipitated solid component can be recovered by a known method including vacuum filtration and pressure filtration.
  • This solid component includes calcium derived from steelmaking slag.
  • FIG. 2 is a flowchart of a calcium recovery method (hereinafter also referred to as “second recovery method”) according to another embodiment of the present invention.
  • the second recovery method further includes a fifth step (step S100) in which the steelmaking slag is immersed in water to obtain slag leachate before the first step (step S110) in the first recovery method,
  • the slag leachate obtained in step 5 is added to the aqueous solution in step 4 (step S160).
  • recovery method is abbreviate
  • the recovery rate of calcium from the steelmaking slag can be further increased.
  • step S100 immersion of steelmaking slag in water
  • the steelmaking slag is immersed in water and calcium is eluted in the water
  • the free lime contained in the steelmaking slag becomes calcium hydroxide by the hydration reaction and is eluted in water.
  • the recovery rate of calcium from the steelmaking slag can be further increased.
  • Slag leachate from which calcium is eluted contains a large amount of calcium hydroxide and thus exhibits strong alkalinity. Therefore, this slag leaching water can be added to the aqueous solution in the fourth step (step S160) in order to increase the pH of the aqueous solution. Moreover, since waste water treatment becomes unnecessary by supplying slag leachate in the fourth step (step S160), the cost of calcium recovery is reduced. At this time, calcium ions in the slag leachate are also precipitated under alkaline conditions as calcium carbonate produced by reaction with bicarbonate ions in the aqueous solution.
  • step S160 Since the calcium contained in the slag leachate is also collected in the fourth step (step S160) after precipitation, the calcium recovery rate from the steelmaking slag is further increased. Moreover, since the calcium in the slag leachate and the calcium in the aqueous solution can be recovered at the same time as the same solid component, a step of combining the recovered calcium compounds is not necessary.
  • the steelmaking slag immersed in water may be the same as the steelmaking slag immersed in the aqueous solution in the first step (step S110), or may be another steelmaking slag.
  • the recovery rate of calcium from the steelmaking slag can be further increased.
  • the fifth step and other steps can be performed simultaneously in parallel, and the working efficiency can be further increased.
  • FIG. 3 is a flowchart of a calcium recovery method (hereinafter also referred to as “third recovery method”) according to still another embodiment of the present invention.
  • the third recovery method further includes a sixth step (step S130) for removing carbon dioxide from the aqueous solution between the second step (step S120) and the fourth step (step S160) in the first recovery method.
  • step S130 for removing carbon dioxide from the aqueous solution between the second step (step S120) and the fourth step (step S160) in the first recovery method.
  • the third recovery method since the input amount of the alkaline substance can be reduced, the recovery of calcium becomes easier and less expensive.
  • the method for removing carbon dioxide from the aqueous solution is not particularly limited.
  • methods for removing carbon dioxide include (1) introduction of gas, (2) decompression and (3) heating.
  • the gas introduced into the aqueous solution preferably has a low reactivity with water, and may be an inorganic gas or an organic gas as long as the reactivity with water is low. Among these, inorganic gas is more preferable because there is little possibility of combustion or explosion even if it leaks to the outside.
  • the inorganic gas include nitrogen, oxygen, hydrogen, argon and helium, and a mixed gas thereof.
  • the mixed gas includes air in an environment in which this step is performed, which includes nitrogen and oxygen in a ratio of approximately 4: 1.
  • the organic gas include methane, ethane, ethylene, acetylene, and propane.
  • the gas that reacts with water chlorine gas, sulfurous acid gas, etc.
  • the above (1) to (3) may be combined. Note that these combinations may be selected in consideration of the supply system of gas and heat, the location, the use of by-product gas in the factory, and the like.
  • the sixth step (step S130) may be performed before the third step (between the second step (step S120) and the third step (step S150)) or simultaneously with the third step (step S150). It may be performed after the third step (between the third step (step S150) and the fourth step (step S160)).
  • slag leachate cannot be obtained in a large amount, even if it is attempted to add slag leachate in the third step (step S150) in the first recovery method or the second recovery method, calcium is sufficiently precipitated. An amount of slag leachate that may be available may not be available. However, by performing the sixth step (step S130) before the third step (step S150), the calcium recovery rate can be further increased even when a small amount of slag leachate is used.
  • FIG. 4 is a flowchart of a calcium recovery method (hereinafter also referred to as “fourth recovery method”) according to still another embodiment of the present invention.
  • the fourth recovery method further includes a sixth step (step S130) for removing carbon dioxide from the aqueous solution between the second step (step S120) and the fourth step (step S160) in the second recovery method. Including. About the 6th process, since it can carry out similarly to the 3rd recovery method, the overlapping description is omitted.
  • FIG. 5 is a flowchart of a calcium recovery method (hereinafter also referred to as “fifth recovery method”) according to still another embodiment of the present invention.
  • the fifth recovery method further includes a seventh step (step S140) in which the solid component is recovered in the middle of the sixth step (step S130) in the third recovery method or the fourth recovery method.
  • FIG. 5 shows a mode in which the fourth recovery method further includes the seventh step (step S140), but the third recovery method can also include the seventh step (step S140) in the same manner. It is.
  • the description which overlaps with the 3rd collection method or the 4th collection method is omitted.
  • a solid component having a high phosphorus compound content and a solid component having a low phosphorus compound content can be obtained separately.
  • step S130 carbon dioxide is removed from the aqueous solution, so that phosphorus in the aqueous solution is precipitated together with calcium.
  • the phosphorus compound to be precipitated include calcium phosphate, calcium hydrogen phosphate, and hydroxyapatite.
  • the content ratio of phosphorus contained in the solid component (hereinafter, also referred to as “initial precipitate”) that precipitates in the initial stage of the sixth step (step S130) is higher.
  • the content ratio of phosphorus contained in the solid component that precipitates later (hereinafter also referred to as “late precipitate”) is lower. Therefore, by recovering the initial precipitate in the middle of the sixth step, the solid component having the higher phosphorus ratio (seventh step) and the solid component having the lower phosphorus ratio (fourth step) are separated. It can be recovered.
  • Phosphorus compounds recovered from steelmaking slag can be reused as phosphorus resources. Therefore, when a solid component having a high phosphorus compound content is recovered, the reuse of phosphorus becomes easy. Moreover, although the calcium compound collect
  • the seventh step (step S140) has a pH of 1 in the sixth step. Preferably, it is performed before 0 rise, more preferably before 0.6 rise, and further preferably before 0.4 rise.
  • the solid component recovered in the fourth step (step S160) has a calcium atom in the total mass of the solid component. Contains 20% by mass or more. Calcium is contained in the solid component in the form of calcium carbonate, calcium bicarbonate or calcium hydroxide. The calcium content in the solid component can be determined by ICP emission spectroscopy.
  • this solid component has a high calcium content, subsequent calcium recovery is easy. Moreover, this solid component can be reused preferably as an iron-making raw material.
  • step S140 since the initial precipitate obtained in the seventh step (step S140) in the fifth recovery method has a high phosphorus content, subsequent phosphorus recovery is easy.
  • the late precipitate obtained in the fourth step (step S160) in the fifth recovery method has a low phosphorus content and a high calcium content, so that subsequent calcium recovery is easy. . Moreover, this late precipitate can be preferably reused as an iron-making raw material.
  • the aqueous solution after recovering the solid component in the fourth step (step S160) is a metal ion containing calcium, phosphorus and manganese.
  • the content of is low.
  • this aqueous solution has a low residual calcium concentration, the load on the environment due to high alkalinity is small, and piping clogging due to calcium precipitation is unlikely to occur. Therefore, even if this aqueous solution is discharged, the load on the environment is small, and wastewater treatment is unnecessary, or the burden of wastewater treatment may be small.
  • this aqueous solution has a low content of metal ions, it can be recovered and safely reused in applications including washing water and cooling water in the factory.
  • Experiments 1 to 6 show examples in which carbon dioxide removal and solid component recovery are performed once.
  • Steelmaking slag having the component ratios shown in Table 1 was prepared.
  • the component of steelmaking slag was measured by ICP emission spectroscopic analysis.
  • the slag was pulverized using a hammer mill so that the maximum particle size was 200 ⁇ m.
  • the maximum particle size of the pulverized slag was confirmed using a laser diffraction / scattering particle size distribution measuring device and a sieve having an opening of 200 ⁇ m.
  • aqueous solution 1 The slag suspension after stirring was allowed to stand to precipitate slag. Thereafter, the supernatant was recovered, and the suspended matter was removed by filtration using a filter (hereinafter, this supernatant is referred to as “aqueous solution 1”).
  • Table 2 shows the components contained in the aqueous solution 1 and the amounts of the respective components measured by ICP emission spectroscopy.
  • the pH of the aqueous solution 1 was 6.4.
  • Example No. 1 Calcium hydroxide was dissolved in water to prepare an aqueous calcium hydroxide solution having a pH of 12.5 and a Ca ion concentration of 530 mg / L. The calcium hydroxide aqueous solution was added to 2 L of the aqueous solution 1. At this time, when 4.3 L of calcium hydroxide aqueous solution was added, the pH increased by 2.1 to 8.5, and when 4.5 L of calcium hydroxide aqueous solution was added, pH increased by 2.6 to 9.0. became.
  • N 2 suspension (Experiment No. 4)
  • the aqueous solution 1 was put into a container with a lid, and N 2 was poured into the space without the aqueous solution 1 at the top at 1 L / min. At this time, the water wheel was rotated at the liquid level so that N 2 was sufficiently suspended.
  • Steps 1 to 3-1 or 1 to 3-2 described above are carried out several times independently, and the pH is 0.3, 0.6, 1.1, 1.6, 2.1 or 2. 6.
  • the pH of the aqueous solution rose (when the pH of the aqueous solution reached 6.7, 7.0, 7.5, 8.0, 8.5, or 9.0, respectively)
  • the solid component precipitated using a filter
  • the aqueous solution 1 containing was filtered under pressure to recover the solid component.
  • the calcium recovery rate in Experiment 1 and Experiment 2 is the amount of calcium measured by the ICP emission spectroscopic analysis method as follows: the amount of calcium contained in the aqueous solution 1 and the amount of calcium contained in the slag leachate 1 The sum was divided by the value.
  • Results Table 4 shows the calcium precipitation conditions, the pH of the aqueous solution 1 at the time of solid component recovery, and the calcium recovery rate.
  • a solid component containing calcium was obtained by raising the pH of the aqueous solution 1.
  • a high recovery rate of 90% or more could be achieved.
  • 35% or more of calcium can be recovered by raising the pH by 0.6 or more
  • 75% or more of calcium can be recovered by raising the pH by 1.1 or more.
  • 90% or more of calcium could be recovered.
  • the recovery rate of calcium by the introduction of the alkaline substance was as high as other methods (removal of carbon dioxide).
  • the pH of the aqueous solution could be easily raised by increasing the amount of alkaline substance input.
  • Table 5 shows the pH and composition of typical solid components obtained by each method when recovered.
  • Experiments 7 to 9 show examples in which carbon dioxide removal and pH increase are combined.
  • Steps 1 to 3-1, 1 to 3-2, or 1 to 3-3 are independently performed a plurality of times, and in each experiment, the pH is 0.3 or 0.4, 0.7 , 1.2, 1.7 or 2.2 (when the pH of the aqueous solution becomes 6.6 or 6.7, 7.0, 7.5, 8.0 or 8.5, respectively) Then, the aqueous solution 2 containing the precipitated solid component was filtered under reduced pressure using a filter, and the solid component was recovered.
  • the initial precipitate is collected before the pH rises by 1.0, and then the late precipitate is collected after raising the pH further. It was possible to separate and recover the solid component having a low content of.
  • Experiment 10 shows another example in which carbon dioxide removal and pH increase are combined and performed separately.
  • Aqueous solution 3 Separation of Steelmaking Slag and Aqueous Solution According to the same procedure as in Experiment 1, an aqueous solution containing carbon dioxide and steelmaking slag were separated, the supernatant was recovered, and the suspended solids were removed by filtration using a filter (hereinafter referred to as "Aqueous solution 3") was collected. The components contained in the aqueous solution 3 and the amounts of the respective components were measured by ICP emission spectroscopy.
  • Precipitation of calcium Indoor air was blown into 3 L of the aqueous solution 3 charged in the container at a rate of 3 L / min while measuring the pH by the glass electrode method. After blowing air for 15 minutes, slag leachate 3 was added to the aqueous solution. After 5 minutes, 10 minutes, 15 minutes and 30 minutes from the start of air blowing, and the amount of slag leachate added to 0.1 L, 0.24 L, 0.4 L and 0.6 L with respect to 1 L of aqueous solution 3 At that time, a part of the aqueous solution 3 was collected, and the amount of calcium dissolved in the aqueous solution 3 was measured by ICP emission spectroscopy.
  • FIG. 6 is a graph showing the pH and calcium dissolution amount in the collected aqueous solution. Since calcium was deposited by removing carbon dioxide by blowing air, the amount of dissolved calcium decreased. Thereafter, calcium was further precipitated by adding slag leachate, and the amount of dissolved calcium decreased rapidly.
  • Table 10 shows the components contained in the aqueous solution 3 after addition (represented as “after precipitation” in the table) and the amount of each component.
  • the calcium recovery method of the present invention can easily increase the recovery rate of calcium in steelmaking slag, it is useful, for example, as a method for recovering calcium resources in iron making.

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PCT/JP2016/001492 2015-03-23 2016-03-16 製鋼スラグからカルシウムを含有する固体成分を回収する方法、および回収された固体成分 WO2016152099A1 (ja)

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CA2980419A CA2980419A1 (en) 2015-03-23 2016-03-16 Method for recovering calcium-containing solid component from steelmaking slag and recovered solid component
US15/560,711 US10287652B2 (en) 2015-03-23 2016-03-16 Method for recovering calcium-containing solid component from steelmaking slag and recovered solid component
MYPI2017703536A MY182970A (en) 2015-03-23 2016-03-16 Method for recovering calcium-containing solid component from steelmaking slag and recovered solid component
KR1020177024574A KR20170130394A (ko) 2015-03-23 2016-03-16 제강 슬래그로부터 칼슘을 함유하는 고체 성분을 회수하는 방법, 및 회수된 고체 성분
MX2017012201A MX2017012201A (es) 2015-03-23 2016-03-16 Metodo para recuperar un componente solido que contiene calcio de la escoria de fabricacion de acero y componente solido recuperado.
BR112017020090-2A BR112017020090A2 (pt) 2015-03-23 2016-03-16 método para recuperação de componente sólido contendo cálcio a partir de escória de fabricação de aço e componente sólido recuperado
CN201680016728.0A CN107406318A (zh) 2015-03-23 2016-03-16 从炼钢渣中回收含有钙的固体成分的方法、以及所回收的固体成分
EP16768006.5A EP3275848A4 (en) 2015-03-23 2016-03-16 Method for recovering calcium-containing solid component from steelmaking slag and recovered solid component
RU2017133114A RU2695173C2 (ru) 2015-03-23 2016-03-16 Способ извлечения твердого компонента, содержащего кальций, из сталеплавильного шлака и извлеченный твердый компонент

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WO2019107115A1 (ja) * 2017-11-30 2019-06-06 日新製鋼株式会社 製鋼スラグからカルシウムを溶出させる方法、製鋼スラグからカルシウムを回収する方法、および製鋼スラグからカルシウムを溶出させる装置
CN110436807A (zh) * 2019-08-22 2019-11-12 武汉钢铁有限公司 一种钢渣表面稳定化的处理方法
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